WO2017064113A1 - Synthèse de graphène sans métal sur des substrats isolants ou semi-conducteurs - Google Patents

Synthèse de graphène sans métal sur des substrats isolants ou semi-conducteurs Download PDF

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WO2017064113A1
WO2017064113A1 PCT/EP2016/074448 EP2016074448W WO2017064113A1 WO 2017064113 A1 WO2017064113 A1 WO 2017064113A1 EP 2016074448 W EP2016074448 W EP 2016074448W WO 2017064113 A1 WO2017064113 A1 WO 2017064113A1
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graphene
inorganic
substrate
process according
cvd
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Zeljko Tomovic
Nils-Eike Weber
Axel Binder
Norbert Wagner
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0209—Pretreatment of the material to be coated by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • Graphene is seen as an exciting material for a number of applications including transparent flexible conducting electrodes and post CMOS electronic devices. To realize these applications, a reliable way of producing large areas of good quality graphene in a consistent fashion is required.
  • One such widely used process is the growth of graphene via chemical vapour deposition on transition metals. The catalytic activity of these transition metal substrates enables simple thermal processes to obtain high quality graphene.
  • the graphene deposition step is carried out by contacting a carbon- containing precursor (such as methane) with the catalytically active transition metal substrate (such as a nickel or copper substrate).
  • a carbon- containing precursor such as methane
  • the catalytically active transition metal substrate such as a nickel or copper substrate.
  • the transition metal substrate is subjected to a thermal pre-treatment in a ⁇ -containing atmosphere, and graphene deposition on the catalytically active transition metal substrate is carried out in the presence of the carbon- containing precursor and hydrogen (hb).
  • A.J. Strudwick et al., ACS Nano, 2015, 9 (1 ), pp. 31 -42 describe the preparation of graphene by CVD on a copper substrate, which acts as a transition metal catalyst and has been subjected to a thermal pre-treatment in the presence of a gaseous oxidant (CO2).
  • CO2 gaseous oxidant
  • the gaseous oxidant can also be present during the graphene deposition step, together with methane acting as the carbon-containing precursor.
  • CVD of graphene on transition metal substrates can be carried out at atmospheric pressure (AP-CVD) or at low pressure (LP-CVD).
  • AP-CVD atmospheric pressure
  • LP-CVD low pressure
  • graphene quality LP-CVD is sometimes superior to AP-CVD.
  • a common technique for the transfer is stabilizing the graphene with a polymer layer such as PMMA, followed by etching off the underlying metal substrate, applying the graphene onto the insulating or semiconducting substrate and final removal of the polymer using an organic solvent.
  • residuals from the polymer and defects due to mechanical stress during the transfer reduce the quality of graphene.
  • the additional process step especially if accompanied by the one-time use of the growth substrate, is a severe cost factor.
  • direct graphene synthesis on insulating or semiconducting substrates is required.
  • US 2015/0232343 relates to a process for preparing graphene on a dielectric substrate via CVD, wherein the deposition chamber is free of plasma during graphene formation.
  • a nickel ingot is positioned upstream of the S1O2 substrate in a CVD reactor. Upon heating, catalytically active nickel is evaporated and supports graphene deposition on the S1O2 substrate.
  • Ariel Ismach et al., Nano Lett. 2010, 10, pp. 1542-1548 describe the preparation of graphene on a S1O2 substrate, wherein graphene is deposited by CVD in a first step on a catalytically active copper film which in turn is positioned on a quartz substrate. Upon thermal treatment, the copper layer is evaporated, thereby leaving the graphene on the quartz substrate.
  • graphene can be prepared on catalytically active nanoparticles or nanowires.
  • the carbon-containing precursor is methane. Due to the presence of CO2, the surface of the Si nanoparticles is partly oxidized, thereby forming a catalytically active non-stoichiometric silicon oxide SiO x surface layer.
  • the same approach is described in US 2015/0093648. According to US 2014/0255500 and EP 2689849 A1 , graphene can be prepared on catalytically active metal particles which are supported on a porous carrier.
  • the object of the present invention is to provide a method for preparing graphene directly on an insulating or semiconducting substrate, thereby avoiding a subsequent graphene transfer from a first substrate on which the graphene had been prepared to a final substrate for electronic or opto-electronic applications.
  • the method should be easy to carry out (e.g. by well-established standard equipment without the need of a specifically adapted reactor design) and provide graphene of sufficiently high quality (e.g. high transmittance in combination with low sheet resistance, low ID/IG ratio).
  • the object is solved by a process for preparing graphene by chemical vapour deposition (CVD), wherein
  • an electrically insulating or semiconducting inorganic substrate is provided in a chemical vapour deposition (CVD) reactor and subjected to a thermal pre-treatment in a hydrogen- containing atmosphere,
  • CVD chemical vapour deposition
  • - graphene is deposited on the insulating or semiconducting inorganic substrate by bringing a gaseous oxidant and a carbon-containing precursor into contact with the insulating or semiconducting inorganic substrate.
  • a graphene of high quality e.g. high transmittance in combination with low sheet resistance, low ID/IG ratio
  • CVD chemical vapor deposition
  • insulating or semiconducting inorganic substrates are in particular those which are used in electronic, opto-electronic or optical devices. Such insulating or semiconducting substrates are known to the skilled person. Typically, the insulating or semiconducting inorganic substrate can be at least partially crystalline or can be amorphous (i.e. a glass). Preferably, the insulating or semiconducting inorganic substrate comprises or may even consist of an inorganic oxide, an inorganic sulphide; an inorganic nitride; an inorganic phosphide, an inorganic carbide, an inorganic halide; an elementary semiconductor such as silicon or germanium; or a mixture or combination thereof.
  • Exemplary inorganic glasses that may be used as a substrate in the process of the present invention include e.g. a S1O2 glass such as fused silica (sometimes also referred to as “fused quartz” or “quartz glass”), a sapphire glass, a borosilicate glass, or an aluminosilicate glass.
  • a S1O2 glass such as fused silica (sometimes also referred to as "fused quartz” or “quartz glass”)
  • a sapphire glass sometimes also referred to as "fused quartz” or “quartz glass”
  • borosilicate glass sometimes also referred to as "quartz glass”
  • aluminosilicate glass e.g., borosilicate glass
  • other inorganic glasses can be used as well.
  • the inorganic substrate comprises an oxide
  • it can be e.g. S1O2, AI2O3, a perovskite oxide (i.e. an oxide having a perovskite structure such as SrTiO-3), Hf02, Zr02, indium tin oxide, a molybdenum oxide, a tungsten oxide, a bismuth strontium calcium copper oxide, or a
  • the inorganic substrate comprises an inorganic sulphide
  • it can be e.g. a molybdenum sulphide or a tungsten sulphide.
  • the inorganic substrate comprises a nitride
  • it can be e.g. S13N4, BN, AIN, or GaN, or a combination or mixture of at least two of these nitrides.
  • the inorganic substrate comprises an inorganic phosphide
  • it can be e.g. an indium phosphide.
  • the inorganic substrate comprises a halide
  • it can be e.g. a fluoride such as an alkaline earth metal fluoride (e.g. CaF2, BaF2 or SrF2).
  • an alkaline earth metal fluoride e.g. CaF2, BaF2 or SrF2.
  • the inorganic substrate comprises a carbide
  • it can be e.g. a silicon carbide.
  • the inorganic substrate comprises an elementary semiconductor, it can be e.g. silicon or germanium.
  • the inorganic substrate may comprise a stoichiometric inorganic compound, which is a compound having an elemental composition whose proportions, averaged over the entire volume of the stoichiometric compound, can be represented by integers.
  • a stoichiometric inorganic compound which is a compound having an elemental composition whose proportions, averaged over the entire volume of the stoichiometric compound, can be represented by integers.
  • Exemplary stoichiometric inorganic compounds are those already mentioned above, such as S1O2, AI2O3 (i.e. stoichiometric oxides), S13N4 (i.e. stoichiometric nitrides) and CaF2 (i.e. stoichiometric fluorides).
  • the insulating or semiconducting substrate consists of the one or more insulating or semiconducting inorganic materials described above.
  • the shape and dimensions of the insulating or semiconducting substrate may depend on the intended electronic or opto-electronic application.
  • the substrate can be a planar substrate. However, non-planar substrates can also be used in the process of the present invention.
  • the substrate is non-porous.
  • the insulating or semiconducting substrate is not part of the CVD reactor but is a separate component positioned inside the reactor cavity (which in turn is defined by the reactor wall).
  • the insulating or semiconducting substrate is positioned on a support member, which may just act as a temporary support during the graphene preparation process or may alternatively represent a permanent support which has been specifically selected in view of the intended electronic or opto-electronic application.
  • a support member on which the substrate might be applied a support made of a semiconductor material, in particular a wafer made of a semiconductor material such as silicon (Si) can be mentioned.
  • the support member is made of Si (e.g.
  • the substrate applied on the support member is made of S1O2 or S13N4.
  • the support member can be made of a first insulating or semiconducting inorganic material (i.e. one of those described above), on which a second insulating or semiconducting inorganic material is provided (wherein the first and second inorganic materials are different from each other) and acts as the substrate for graphene deposition.
  • the insulating or semiconducting substrate on which the graphene is to be deposited is positioned in a chemical vapour deposition (CVD) reactor.
  • CVD reactors are commonly known.
  • the CVD reactor can be a hot wall reactor.
  • the CVD reactor design is compatible with low- pressure CVD (i.e. a LP-CVD reactor).
  • the process of the present invention can also be carried out in a CVD reactor designed for deposition at atmospheric pressure (AP-CVD reactor).
  • AP-CVD reactor atmospheric pressure
  • graphene of high quality can be obtained in the absence of any transition metal catalyst.
  • no transition metal catalyst in particular no Cu- or Ni-containing metal catalyst
  • the insulating or semiconducting substrate is not in contact with a transition metal catalyst.
  • it is also possible that a transition metal catalyst is present in the CVD reactor.
  • the insulating or semiconducting inorganic substrate is subjected to a thermal pre-treatment in a hydrogen-containing atmosphere prior to graphene deposition.
  • the hydrogen-containing atmosphere may consist of hydrogen or may contain additional gaseous components.
  • the hydrogen content of the gas atmosphere used for the thermal pre- treatment is at least 30 vol%, more preferably at least 50 vol%, or at least 70 vol%.
  • the hydrogen-containing gas atmosphere may comprise an inert carrier gas (e.g. a noble gas).
  • the gas atmosphere of the thermal pre-treatment step may contain an oxidant.
  • no gaseous or supercritical oxidant is fed into the CVD reactor during the thermal pre-treatment of the inorganic substrate.
  • the thermal pre-treatment includes heating of the inorganic substrate at a temperature of at least 500°C.
  • Exemplary temperature ranges are from 500°C to 2500°C, more preferably from 525°C to 1500°C, even more preferably from 550°C to 1300°C or 700°C to 1300°C or 700°C to 1075°C.
  • Different heating programs can be used for thermal pre-treatment of the inorganic substrate.
  • the substrate can be heated at a constant heating rate until a temperature T1 is reached, the temperature T1 may then be kept constant during the entire pre- treatment step or may be kept constant just for a while before being changed (either increased or decreased) again.
  • Other heating programs can be used as well.
  • the carbon-containing precursor can already be present in the CVD reactor during the thermal-pre-treatment step.
  • the substrate can be heated directly or indirectly. Just as an example, heating the substrate can be achieved by heating the CVD reactor to an appropriate temperature.
  • the time period for which the insulating or semiconducting substrate is subjected to a thermal pre-treatment may vary over a broad range. Just as an example, the substrate might be subjected to a thermal pre-treatment for at least 15 minutes, more preferably at least 60 minutes, or at least 270 minutes.
  • a graphene seed material can be provided on the insulating or semiconducting substrate.
  • the graphene seed material can be e.g. an externally prepared graphene or graphene oxide (e.g. prepared via chemical or mechanical exfoliation, CVD, ... etc.).
  • the externally prepared graphene or graphene oxide acting as a seed material has lateral dimensions which are significantly smaller than those of the insulating or semiconducting substrate.
  • Polyaromatic hydrocarbons e.g. triphenylene, perylene, pyrene
  • Such polyaromatic hydrocarbons acting as a seed material can be provided on the substrate by commonly known methods, such as spin coating.
  • a further substrate pre-treatment step is carried out in between the thermal-pre-treatment step and the graphene deposition step, such as a substrate polishing or etching step or providing a graphene seed material on the substrate.
  • the graphene deposition step directly follows the thermal pre-treatment step.
  • graphene is deposited on the insulating or semiconducting inorganic substrate by bringing a gaseous oxidant and a carbon-containing precursor into contact with the inorganic substrate.
  • the term "graphene” is not limited to a single layer graphene but also encompasses a few-layer graphene having e.g. up to fifty graphene layers or up to twenty graphene layers or up to five graphene layers.
  • the oxidant which is present in the graphene deposition step is selected from carbon oxides (in particular CO2 and CO), nitrogen-containing oxides (in particular NO, NO2, N2O), H2O, O2, air, and any mixture thereof. More preferably, the gaseous oxidant is CO2 or CO or a mixture thereof.
  • the gaseous oxidant can be diluted by a carrier gas, preferably an inert carrier gas such as a noble gas or nitrogen (N2).
  • the carbon-containing precursor is a hydrocarbon compound, which can be e.g. a saturated or unsaturated or an aromatic hydrocarbon.
  • the hydrocarbon compound may contain a functional group.
  • the hydrocarbon compound can be a linear, a branched or a cyclic hydrocarbon compound.
  • the unsaturated hydrocarbon precursor compound can be an alkene or an alkyne.
  • a preferred alkyne is acetylene.
  • benzene can be mentioned.
  • gaseous compounds can also be present in the CVD reactor during the graphene deposition step, such as a compound for heteroatom (e.g. nitrogen- or boron-)doping of graphene, e.g. ammonia or an amine or a boron halide (e.g. BC ).
  • a compound for heteroatom e.g. nitrogen- or boron-
  • hydrogen might also be present during the graphene deposition step.
  • no hydrogen is fed into the CVD reactor during the graphene deposition step.
  • the volume ratio of the gaseous oxidant and the carbon-containing precursor is typically within the range of from 1/2 to 1/50, more preferably of from 1/5 to 1/20.
  • the volume ratio of the gaseous oxidant and the carbon-containing precursor can be adjusted e.g. via their feeding rates into the CVD reactor.
  • the gaseous oxidant and the carbon-containing precursor can be fed into the CVD reactor by means commonly known to the skilled person.
  • the oxidant and the precursor are stored in containers which are outside the CVD reactor and are then fed from the external containers into the CVD reactor.
  • the oxidant or the carbon-containing precursor may already be in a gaseous state when stored in an external container.
  • gaseous oxidant or the carbon-containing precursor or both is/are generated in situ in the CVD reactor.
  • a gaseous oxidant water vapour
  • TCVD at which the chemical deposition of the graphene is carried out can vary over a broad range.
  • TCVD can be e.g. at least 450°C, more preferably at least 525°C, even more preferably at least 700°C or at least 950°C.
  • the upper limit may depend on the thermal stability of the CVD reactor wall material.
  • Appropriate temperature ranges can be adjusted by the skilled person. Exemplary temperature ranges are from 500°C to 2500°C, more preferably from 550°C to 1300°C, even more preferably from 700°C to 1300°C or from 950°C to 1075°C.
  • the temperature in the CVD reactor can be measured and controlled by means which are commonly known to the skilled person. Appropriate heating elements for CVD reactors are known to the skilled person. Furthermore, it is generally known to the skilled person how a CVD reactor is to be designed for preparing graphene by chemical vapour deposition.
  • the pressure adjusted in the CVD reactor during the graphene deposition step may vary over a broad range.
  • the process of the present invention is suitable for low-pressure CVD (LP-CVD) as well as for atmospheric pressure CVD (AP-CVD).
  • An appropriate reactor pressure for LP-CVD is e.g. within the range of from 0.01 to 500 mbar, more preferably from 0.1 to 200 mbar, even more preferably from 1 to 50 mbar or from 3 to 10 mbar.
  • the CVD reactor may then be cooled down (e.g. to room temperature).
  • the feed of the carbon-containing precursor is stopped when cooling down the CVD reactor.
  • feeding of the gaseous oxidant into the CVD reactor can be continued while cooling down.
  • the gaseous oxidant feed is stopped and one or more other gases such as hydrogen are fed into the CVD reactor while cooling down.
  • the present invention further relates to a composite comprising an insulating or semiconducting inorganic substrate and a graphene applied thereon, the composite obtainable by the process as described above.
  • the present invention further relates to a process for manufacturing an electronic, optoelectronic or optical device wherein a composite comprising an insulating or semiconducting inorganic substrate and a graphene applied thereon is prepared as described above, and the composite is incorporated into an electronic, opto-electronic or optical device. No transfer of graphene from a first substrate to a second substrate is needed in said manufacturing method.
  • Exemplary devices include capacitors, energy-storing devices (such as supercapacitors), field effect transistors, photovoltaic devices, light-emitting diodes, transparent electrodes, etc.
  • a CVD chamber comprising a tube furnace (10 cm tube diameter) made from quartz glass was used.
  • Gas flows were controlled by mass flow controllers. Pressure was measured via a Pfeiffer vacuum Pirani gauge.
  • Raman maps were carried out with a NT-MDT NTEGRA spectrometer. Samples were measured in either a combined AFM-Raman measuring configuration or with a Raman only configuration. Both configurations use a 100x optical objective with an average spot size of around 1 ⁇ . The laser wavelength used in all measurements is 441 .6 nm. The diffraction grating used had 600 lines/cm and has a spectral resolution of 1 cm- 1 at this excitation wavelength. During all measurements there was no observation of the Raman laser altering the sample composition (observed by monitoring the spectra from a single point repeatedly over time during the focusing process). Fits to the G band were carried out using a standard
  • Sheet resistance of the deposited graphene film was determined by a four-point-probe technique.
  • Optical transmittance was determined with a Perkin Elmer UV-Vis-NIR Spectrometer Lambda 750, corrected by the influence of the substrate.
  • quartz glass As a substrate for graphene deposition by CVD, quartz glass was used. The glass substrate was cleaned prior to the CVD process in acetone and isopropanol in an ultrasonic bath, and was blown dry with gentle argon stream. After evacuation to the base pressure of the system ( ⁇ 0.005 mbar) and a leak test ( ⁇ 0.1 mbar/h) the glass substrate was annealed under a hydrogen atmosphere (hydrogen 50 seem, ⁇ 0.1 mbar) to the growth temperature of 1050°C. To avoid temperature overshoot the ramp is reduced from 20 K/min to 10 K/min for the last 50 °C. At the temperature of the CVD step, i.e.
  • the process gases are switched to a mixture of CH4, i.e. the carbon-containing precursor, and CO2, i.e. the gaseous oxidant (CO2 : CH4 gas mixture; 3 : 30 seem).
  • the pressure (5 mbar) in the reactor tube is controlled by a valve downstream, regulating the pump rate of the rotary pump.
  • the furnace is cooled down under a hydrogen atmosphere (hydrogen 50 seem, ⁇ 0.1 mbar).
  • the temperature profile is shown in Figure 1.
  • Comparative Example 1 the same substrate as in Example 1 was used. After evacuation to the base pressure of the system ( ⁇ 0.005 mbar) and a leak test ( ⁇ 0.1 mbar/h) the glass substrate was annealed under a hydrogen atmosphere (hydrogen 50 seem, ⁇ 0.1 mbar) to the growth temperature of 1050°C. To avoid temperature overshoot the ramp is reduced from 20 K/min to 10 K/min for the last 50 °C. At the temperature of the CVD step, i.e. 1050°C, the process gases are switched to a mixture of CH4, i.e. the carbon-containing precursor, and hydrogen (H2 : CH4 gas mixture; 150 : 50 seem).
  • the pressure (5 mbar) in the reactor tube is controlled by a valve downstream, regulating the pump rate of the rotary pump. After 60 minutes reaction time, the furnace is cooled down under a hydrogen atmosphere (hydrogen 50 seem, ⁇ 0.1 mbar). The temperature profile is shown in Figure 4.
  • gaseous oxidants have been used in the prior art during a CVD graphene deposition step in combination with substrates being made of a catalytically active material that can react to some extent with the oxidant (e.g. a Ni substrate that may form a reactive non-stoichiometric NiO x layer, or Si nanoparticles that may form a reactive non- stoichiometric SiO x layer).
  • a catalytically active material that can react to some extent with the oxidant (e.g. a Ni substrate that may form a reactive non-stoichiometric NiO x layer, or Si nanoparticles that may form a reactive non- stoichiometric SiO x layer).
  • a substrate made of an insulating or semiconducting inorganic compound such as S1O2, AI2O3 or S13N4 is expected to be relatively inert or non-reactive towards the gaseous oxidant during the CVD step, which in turn would mean that the gaseous oxidant is expected to react with the graphene prepared from the carbon-containing precursor.
  • the use of a gaseous oxidant in combination with the insulating or semiconducting substrate is surprisingly providing a graphene of high quality in standard CVD reactors even at low pressure (LP-CVD), whereas the use of hydrogen in the absence of a gaseous oxidant during the CVD step failed to produce graphene by LP-CVD on an insulating substrate.
  • Example 1 was repeated. However, instead of a quartz glass substrate, a sapphire glass substrate was used, whereas all other process parameters were identical to those of Example 1 .
  • Example 1 was repeated. However, instead of a quartz glass substrate, a S1O2 film on a Si wafer was used (S1O2 representing the insulating substrate, and the wafer representing the support member for the insulating substrate), whereas all other process parameters were identical to those of Example 1 .
  • S1O2 representing the insulating substrate
  • the wafer representing the support member for the insulating substrate
  • all other process parameters were identical to those of Example 1 .
  • graphene was successfully deposited on the insulating substrate.
  • the deposited graphene was characterized by Raman spectroscopy.
  • the intensity ratio of the D peak to the G peak i.e. ID/IG) is about 0.5, which indicates a relatively low number of defects.

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Abstract

La présente invention concerne un procédé de préparation de graphène par dépôt chimique en phase vapeur (CVD), un substrat inorganique isolant ou semi-conducteur étant utilisé dans un réacteur de dépôt chimique en phase vapeur (CVD) et soumis à un prétraitement thermique dans une atmosphère contenant de l'hydrogène, et du graphène étant déposé sur le substrat inorganique en mettant en contact un oxydant gazeux et un précurseur contenant du carbone avec le substrat inorganique.
PCT/EP2016/074448 2015-10-15 2016-10-12 Synthèse de graphène sans métal sur des substrats isolants ou semi-conducteurs WO2017064113A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109402605A (zh) * 2018-11-15 2019-03-01 中国人民大学 一种大面积层数可控的石墨烯与六方氮化硼异质结的制备方法
CN110282617A (zh) * 2019-07-26 2019-09-27 北京石墨烯研究院 一种石墨烯粉体及其制备方法
CN111948423A (zh) * 2020-08-24 2020-11-17 山东理工大学 一种基于石墨烯的流速传感器光学芯片及其应用
WO2021115596A1 (fr) * 2019-12-11 2021-06-17 Jozef Stefan Institute Procédé et appareil de dépôt de nanostructures de carbone
US11618681B2 (en) 2021-06-28 2023-04-04 Wisconsin Alumni Research Foundation Graphene nanoribbons grown from aromatic molecular seeds

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120282489A1 (en) * 2011-05-06 2012-11-08 Samsung Electronics Co., Ltd. Direct graphene growing method
US20130243969A1 (en) * 2012-03-14 2013-09-19 Po-Yuan TENG Chemical vapor deposition of graphene on dielectrics
EP2689849A1 (fr) 2012-07-26 2014-01-29 Samsung Electronics Co., Ltd Catalyseur de reformage CO2, son procédé de préparation et procédé de reformage de CO2
US20140255500A1 (en) 2013-03-11 2014-09-11 Samsung Electronics Co., Ltd. Method for preparing graphene
WO2014174133A1 (fr) * 2013-04-22 2014-10-30 Universitat De Barcelona Procédé pour la production contrôlée de graphène à très basse pression et dispositif de mise en oeuvre de ce procédé
US20150093648A1 (en) 2013-09-30 2015-04-02 Samsung Electronics Co., Ltd. Composite, carbon composite including the composite, electrode, lithium battery, electroluminescent device, biosensor, semiconductor device, and thermoelectric device including the composite and/or the carbon composite
US20150232343A1 (en) 2014-02-18 2015-08-20 Corning Incorporated Metal-free cvd coating of graphene on glass and other dielectric substrates

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120282489A1 (en) * 2011-05-06 2012-11-08 Samsung Electronics Co., Ltd. Direct graphene growing method
US20130243969A1 (en) * 2012-03-14 2013-09-19 Po-Yuan TENG Chemical vapor deposition of graphene on dielectrics
EP2689849A1 (fr) 2012-07-26 2014-01-29 Samsung Electronics Co., Ltd Catalyseur de reformage CO2, son procédé de préparation et procédé de reformage de CO2
US20140255500A1 (en) 2013-03-11 2014-09-11 Samsung Electronics Co., Ltd. Method for preparing graphene
WO2014174133A1 (fr) * 2013-04-22 2014-10-30 Universitat De Barcelona Procédé pour la production contrôlée de graphène à très basse pression et dispositif de mise en oeuvre de ce procédé
US20150093648A1 (en) 2013-09-30 2015-04-02 Samsung Electronics Co., Ltd. Composite, carbon composite including the composite, electrode, lithium battery, electroluminescent device, biosensor, semiconductor device, and thermoelectric device including the composite and/or the carbon composite
US20150232343A1 (en) 2014-02-18 2015-08-20 Corning Incorporated Metal-free cvd coating of graphene on glass and other dielectric substrates

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
A.J. STRUDWICK ET AL., ACS NANO, vol. 9, no. 1, 2015, pages 31 - 42
ARIEL ISMACH ET AL., NANO LETT., vol. 10, 2010, pages 1542 - 1548
H.J. SONG ET AL., NANOSCALE, vol. 4, 2012, pages 3050 - 3054
I.H. SON ET AL., ACS NANO, vol. 8, 2014, pages 9224 - 9232
I.H. SON ET AL., NATURE COMMUNICATIONS, vol. 6, 2015, pages 7393
IN HYUK SON ET AL: "Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density", NATURE COMMUNICATIONS, vol. 6, 25 June 2015 (2015-06-25), pages 7393, XP055264508, DOI: 10.1038/ncomms8393 *
J. ET AL., J. AM. CHEM. SOC., vol. 133, 2011, pages 17548 - 17551
J. SUN ET AL., J. APPL. PHYS., vol. 111, 2012, pages 044103
M.A. FANTON ET AL., ACS NANO, vol. 5, 2011, pages 8062 - 8069
MARK A. FANTON ET AL: "Characterization of Graphene Films and Transistors Grown on Sapphire by Metal-Free Chemical Vapor Deposition", ACS NANO, vol. 5, no. 10, 11 September 2011 (2011-09-11), US, pages 8062 - 8069, XP055264491, ISSN: 1936-0851, DOI: 10.1021/nn202643t *
P.-Y. TENG ET AL., NANO LETT., vol. 12, 2012, pages 1379 - 1384
W.C. YEN ET AL., SCIENTIFIC REPORTS, vol. 4, no. 4739, 2014
Z. LIU ET AL., NANO LETT., vol. 15, no. 9, 2015, pages 5846 - 5854

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109402605A (zh) * 2018-11-15 2019-03-01 中国人民大学 一种大面积层数可控的石墨烯与六方氮化硼异质结的制备方法
CN110282617A (zh) * 2019-07-26 2019-09-27 北京石墨烯研究院 一种石墨烯粉体及其制备方法
WO2021115596A1 (fr) * 2019-12-11 2021-06-17 Jozef Stefan Institute Procédé et appareil de dépôt de nanostructures de carbone
CN111948423A (zh) * 2020-08-24 2020-11-17 山东理工大学 一种基于石墨烯的流速传感器光学芯片及其应用
US11618681B2 (en) 2021-06-28 2023-04-04 Wisconsin Alumni Research Foundation Graphene nanoribbons grown from aromatic molecular seeds

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